Manufacture of halogenated polymers



July 27, 1954 J. s. REARICK' MANUFACTURE 0F HLOGENTED POLYMERS Filed Ma'rch 26, 1952 Patented July 27, 1954 UNITED STAT 'OFFICE John S. Reariclq, Ironia, N. 3., assignor to The M. W. Kellogg Company, Jersey City, N. J., a

corporation of Delaware Application March 26, 1952, Serial No. 278,532

(Cl. 2GB-87.5)

16 Claims.

This invention relates to the manufacture of halocarbons. In one of its aspects this invention relates to the polymerization of perhalo-oleiins. In another aspect the invention relates particularly to the copolymerization of trifluorochloroethylene with another perhalogenated olefin in a continuous manner to produce a normally solid polymeric compound of high chemical and physical stability. This application is a continuationin-part of application Serial No. 20,612, filed April 13, 1948, now Patent No. 2,609,804.

Under Suitable reaction conditions trifluorochloroethylene can be polymerized to produce a normally solid polymer or plastic of good physical and chemical properties and suitable for molding articles of manufacture and for various other uses. At the present time, polymerization oi triuorochloroethylene to produce solid polymers is effected in a batch manner in a bomb type reaction vessel. Accordingly, the monomer is introduced into the bomb together with a suitable promoter and the temperature of the bomb maintained at about -16 C. or 17 C. for a period of about seven days. The monomer is converted to a porous plug of the solid polymer in the reaction vessel with approximately 30 to 5G per cent yield of polymer based on the monomer charged. The unreacted monomer is occluded in the interstices of the porous plug and is removed therefrom by heating the reaction vessel under subatmospheric pressure so that the monomeil is evaporated from the polymer plug. After the monomer has been thus evaporated, the plug is removed from the reaction vessel and broken into chips or granules.

The apparatus currently employed to effect the process described above is a cylindrical vessel or bomb approximately 6 inches in inside diameter, which is placed in a cooling bath. Because of the poor heat transfer characteristics of the polymer it is necessary to maintain this cooling bath at a temperature materially below the optimum pclymerization temperature to avoid overheating of the material in the center of the reaction vessel. Experiments in vessels of smaller diameter have indicated that the bath temperature can ce increased, and hence the average temperature of the material, Without increasing the maximum temperature of the material at the center of the vessel. Because of the increase of the average temperature, the rate of polymerization is greater. which factor results in a shorter period of time to obtain an economical yield of product. There is also indication that the quality of the solid polymer produced is improved as a result of the greater uniformity of temperature characterized by smaller vessels. However, reduction in the diameter of the vessel reduces the amount of the material which can be produced for a given charge since the length of the vessel must be limited to enable easy removal of the solid polymer from the vessel. It is, therefore, desirable to provide a method and apparatus for overcom ing the above diiiculties involved in the production of normally solid polymers of triiiuorochloroethylene.

The object of this invention is to provide a continuous process for the polymerization of perhalogenated olens to produce normally solid polymers.

A more specic object of this invention is to provide a process for the manufacture of a normally solid copolymer of perhalogenatd oleins.

Still another object of this invention is to provide a method and apparatus for more adequate control of the temperature of reaction in the copolymerization of trifluorochloroethylene than is at present practiced.

A further object of this invention is to provide a process and apparatus for the improvement in the quantity and reproducibility of normally solid copolymers of trifluorochloroethylene.

It is still a further object of this invention to provide a process to increase the yield of normally solid copolymers of triuorochloroethylene.

Various other objects and advantages of the present invention will become apparent to those skilled in the art from the accompanying description and disclosure.

As herein employed, a perhalocarbon copolymer is deiined as a polymer consisting substantially of carbon and halogen any degree of saturation, and with less than about 2 weight per cent of impurities, such as hydrogen, obtained from the promoter or solvent employed. A perhalo-oleiin is dened as a perhalocarbon with ans degree of unsaturation, consisting of halogen and carbon and as regards this invention the halogens are preferably fluorine and chlorine.

In accordance with the continuous and improved process of this invention, a saturated fluorochlorocarbon is dechlorinated under suitable conditions of dechlorination in the presence v of a metallic dehalogenating agent to produce a perluorohalomlen as a monomer for the subsequent polymerization reaction. The dechlorination reaction is carried out in the presence of a suitable solvent together with a minor proportion of a metal halide, which may ce that formed during the dechlorination reaction, and accord ing to the preferred method of operation of this invention the solvent is one which is capable oi dissolving the metal halide formed by the dehalogenaticn reaction and is higher boiling than the monomer produced. An eflluent comprising the desired monomer and including unreacted saturated halocarbon and solvent is passed to a fractional distillation system in which substantiall;7 pure monomer is recovered. Saturated halccarbon feed and solvent recovered from the monomer is returned to the dechlorination reaction zone. The monomer after further purification is passed to a polymerization reaction zone in which it is contacted with another perhalogenated olefin prepared in a similar manner and is subjected to Suitable reaction conditions to convert the monomers to a normally solid copolymer. The monomers are maintained in the liquid phase and under a sufficient degree of agitation in the polymerization reaction zone so that the normally solid copolymer formed by the reaction, which is insoluble in the monomer, is caused to form a slurry or suspension therewith in the reaction zone. In ei'ecting' the reaction to produce the solid copolymer' a suitable promoter material is used to promote the reaction. A portion of the liquid phase in the polymerization reaction zone is continuously removed therefrom as a slurry or suspension containingl solid copolymer particles and is passed to separa-- tion zone in which the solid'particles are removed and the recovered unreacted monomers are recycled to the polymerization reaction sone. A portion of the monomers recovered from the slurry or suspension maybe returned to the distillation sy"- tem for repurication. The solid copolymer is recovered as powder or granules and is treated to remove entrained monomers therefrom. The homopolymerization of a perhalogenated olen is carried out in a similar manner.

Preferably, the slurry or suspension from the reaction zone is cooled and the rate of withdrawal and degree of cooling is controlled to maintain the reaction zone temperature at the desired value. The fluid nature of the slurry or suspension and the agitation in the reaction zone assures uni form temperatures for the polymerization reaction, While the recycle of cooled unreacted monomers removes the heat of polymerization,

In one aspect this invention relates to the polymerization of a perhalogenated ol'en containing fluorine in a reaction zone by introducing the monomer alone or together with another co monomer into the reaction zoneand polymerizing the monomer at a temperature appropriate to produce a normally solid product or plastic in the presence of a suitable promoter which is effective for the promotion of polymerization at a pressure sufficient to maintain the system in the liquid phase to produce particles of solid polymer in suspension in the liquid phase of monomer at the temperature of polymerization and separating and recovering finely divided particles of solid polymer from the suspension of solids in monomer as a produce of the process. This type of polymerization in Which the solid particles o1E polymer are produced in suspension in liquid monomer is characteristic only of those systems in which the solid polymer is substantially insoluble in the monomer. rEhis type of polymerization is also applicable only to those polymerization systems in which the rate of polymerization is suiiciently slow that the heat of polymerization can be re moved adequately and that positive control can be maintained on the amount of'ccnversion, i. e., concentration of solid polymer suspended in the monomer. Consequently, those monomers which produce a solid polymer which is soluble in the monomer cannot be employed in the present invention. It has been found that the insolubility of the polymer in liquid monomer is characteristic of the halogenated polymers of the olens containing luorine. Although. some hydrogen may be permitted in the monomer it is preferred to limit the hydrogen atoms of the monomer to not more than the number oi carbon atoms, since hydrogen` in the polymer tends to increase its solubility in the monomer.

Since the rate of reaction is an important factor in the adaptation of this system to the polymerization of halogenated monomers, only those polymerization systems which have a controllable rate or reaction can be employed. For example, under normal operating conditions the homopolymerisation of tetraluoroethylene is so fast that it is substantially impossible to remove the. heat of polymerization at an adequate rate and it is substantially impossible to control thefrate of reaction such that a suspension of'poly-F mer in monomer is formed. The rmerizationA of tetrafluoroethylene usually proceeds at such a rate that a solid mass of polymer is produced inI avery short period of time which makes it impossi ble to form a suspension ci' polymer vin monomer'. On the other hand, the hornopolymerization o." truorochloroethylene proceeds at a controllable` rate at normal conditions whereby a suspensionv of solid polymer in liquidY monomer can be produced and the resulting polymer recovered froml the suspension. The rate of reaction is also such that the heat of polymerization can be adelinately.4 removed during the polymerization. l

The abovetwo factors severelylimit-the syste-ms to which suspensions of polymer in liouid mer can be formed and recovered. t has been found that such systems comprise essentiallvsys4 tems for the homopolymeriaation of iorochlorcethylene and systems for thecopclymeri ation. of triiluorochlorcethylenewith other hal ,ted duerme-containing olefins having no more hydrogen atoms than the number. of carbon atoms; Such copolymerization systems inciude theA coby polymerization of triiluorochloroethylene2 with: tetrafluoroethylene, perfluoropropene, periluoro-,i butadiene, vinylidene fluoride,- triluoroethylene, monofluoromonochloroethylene, monochlk odifluoroethylene and dichloroporfluoropropene. These copolymerizations proceed at a reasonable rate to produce a good yield of solid polymer in suspension in the liquid monomer at a controllable rate of reaction. In the copolymerizationit is usually preferred to employ from 5 to 95 weight per cent of the comonomer with t iuoroohlcroethylene, preferably l5 to 85 weight per cent of the ccmonomer, The conditions of polymeriza-v tion of the copolymers of triluorochloroethylene are substantially the same as for the homopolymerization of trifluorochloroethylene, Th f lowing discussion of genera-l application or t present invention to the polymerization of uorochloroethylene applies substanlially to theY above copolymerization systems.

For a better understanding o the present invention, reference will be made to the accompanying drawing which diagrammatically illustratesan arrangement of apparatus in elevation which may be used for the production of normally solid plastic homo and copolymers of triflucrochloroethylene. The principal pieces of apparatus for effecting the process depictedl in the drawing comprise a dehalogenator 6, a polymerization retinuously passed through conduit 3 to dehalo- 1 genator E. A metallic dechlorinating agent, such as zinc dust, is continuously or intermittently introduced through conduit E into reactor S. Although zinc is preferred, various metal dechlormating agents may be used, such as tin, rnag nesium, and iron, without departing from the scope of this invention. A suitable solvent or diluent is continuously or intermittently introduced into feed conduit 3 through conduit d, or alternatively directed into dehalogenator il by means not shown. In the discussion of the process of the drawing, the solvent used in the dechlorination of trichlorotriiiuoroethane is methyl alcohol. The amount of metal dechlorinating agent introduced into dehalogenator 6 is equivalent to at least the theoretical amount necessary for removal of two halogen atoms from the halocarbon. Preferably, an excess dechlorinating agent is used in effecting the dechlorinating reaction and the excess may be as much as l per cent or more. The amount of solvent may vary depending upon the reaction conditions, the quantity generally being less for superatinospheric than for atmospheric pressures, a suitable quantity for operation at atmospheric pressure being 65 per cent of the weight of the halocarbon charged. The mixture of halocarbon and solvent is vigorously agitated by conventional means, such as mechanical stirrer 3, to suspend the metal dechlorination agent in the liquid mixture in the lower portion of reactor ii. Required temperatures are maintained in the liquid phase of dehalogenator by conventional means, such as heating or cooling coils Si or a jacket through which a heat exchange medium is passed at the desired temperature. For a temperature below about 0 C., a light naphtha may conveniently be used. Water may be used for higher temperatures. Outlet conduit ll is used for discharging the liquid contents of dehalogenator 0.

For the deehlorination of trichlorotriuoroethane to triluorochloroethylene, pressures between atmospheric and about 300 or 400 pounds per square inch gage are employed, preferably a pressure between about 20 and about 200 pounds per square inch gage, and a particularly suitable pressure is about 180 pounds per square inch gage. In the preferred form or the invention, the pressure should be such at any given temperature to permit vaporization of the triiiuorochloroethylene from the liquid phase in dehalogenator 6 without substantial vaporization of the other constituents of the reaction mixture. A suitable temperature for the dehalogenation is between about 0 C. and 200n C. It is preferred to use a temperature between about lo and about 150 C., usually about 115 C. for operation at 180 pounds per square inch gage. At the higher temperatures the rate of reaction is increased, which in most instances is desirable. However, excessive temperatures cause undesirable side reactions.

In starting up the dehalogenation reaction a small proportion of a metal halide, such as zinc chloride, is introduced into dehalogenator i to promote or start the dehalogenation reaction.

The metal halide may be introduced separately, or in admixture with the dehalogenating agent through conduit 5.

Suitable solvents or diluents for the dehalogenation step comprise methyl, ethyl, n-propyl, and n-butyl alcohols; dicxane, glycerol, butyl Carbitol, the Cellosolves and water. Other known solvents or diluents may be used, if desired, without departing from the scope of this invention.

0 The preferred solvents are methyl alcohol and ethyl alcohol.

Since the temperature and pressure conditions which are maintained in dehalogenator 6 according to the preferred embodiment of this invention are such that the halogenated olefin formed therein as the desired product is vaporized, the olefin passes upward together with entrained and vaporized saturated halocarbons and solvent through a rectification column il. The major proportion of the halocarbon and solvent are retained in the liquid phase in dehalogenator 5. The upper portion of the recticaticn column li is maintained at a temperature substantially lower than the temperature of the liquid phase of dehalogenatol` 6, preferably at least C. lower. The top temperature of column i i is maintained at the desired level by indirect heat eX- change means l2 or by rerluxing a portion of liqueiied overhead product. In rectiiication column i i, methyl alcohol solvent and trichlorotrirluoroethane are condensed and iiow downward back into the dehalogenator 6, while the monomer is removed therefrom through conduit i3. Since rectification column li eects only a partial separation, the vaporous monomer stream in conduit i3 may contain minor amounts of higher-boiling by-products, such as diiiuoromonochloroethylene, and unreinoved trichlorotriluoroethane and methyl alcohol. Lower boiling byproducts, such as tetrafluoroethylene, may also accompany the monomer.

A typical composition of the triiiuorochloroethylene-containing stream in conduit i3 is shown below in Tab-le I for operation of dehalogenator t at a superatmospheric pressure or" 87.5 pounds per square inch gage and rectification column il at a top temperature of about 24 C.

The monomer-containing stream is passed through conduit i3 to a cooler ifi, wherein it is liquefied, and thence to a fractional distillation column i6. As previously mentioned, a portion of the liqueed eiiiuent in conduit i3 may be returned by means not shown to the upper portion of rectification column i! as liquid redux therefor to aid in maintenance of the required top temperature.

The subsequent treatment of the effluent in conduit i3 is an important feature of the process since the purincation of the monomer triuorochloro-ethylene by the removal oi the alcohol solvent and saturated perhalocarbon is essential in order to obtain satisfactory yields and reproducible results in the polymerization effected in reactor 44. To eiect the puriiication of the monomer, liquid from conduit i3 is, in one embodiment of this invention, introduced into fractional 7 distillation column i6. This column is maintained at a temperature and pressure corresponding to that required to pass monomer overhead and to recover the solvent and unreacted saturated halocarhon as a bottoms product. If

superatmospheric pressures are employed during the dehalogenation in unit 5, the pressure Of the liquid in conduit i3 may he decreased upon introduction into distillation column iii to aid in the fractional distillation and lower the teniperatures required therein. Both atmospheric and superatmospheric distillations are feasible and in some cases superatmospheric distillation may ce preferred. A top temperature of about -2l C. is appropriate for atmospheric distillation in column le. Indirect heat exchange element Il is provided in the lower portion of column I6 as a means for controlling the temperature of the cottoms product, te temperature of Which is about C. at atmospheric pressure. Element Il may comprise an internal coil within column l5 or a conventional external reooiler. Upon distillation, the monomer is removed from column I6 through conduit lil together with a relatively minor proportion of unremoved saturated halocaroon and also in some cases small amounts of methyl alcohol. The vaporous effluent is passed through conduit it to a conventional cooler1 or condenser ill wherein the eluent is condensed. From cooler l, the eiluent is passed to an accumulator 2l in which condensate is collected. A portion ci the condensate is returned to column it through conduit 'i2 as liquid reflux therefor. internal cooling means (not shown) be positioned Within the upper portion of column i6 to aid in reiuxing of the distillation column and may loe used in addition to, or alternatively to, condensate returned through conduit 22.

rEhe bottoms product from distillation column I6 is removed therefrom through outlet conduit 23 and is returned by means of a pump (not shown) through conduits 23 and 2li to dehalogenator i. rihe bottoms product comprises the major proportion of the solvent and saturated halocaroon in the monomer-containing stream of conduit i3.

Analysis of a typical overhead product of column le when it is operated at a top temperature of about d" C. and a kettle temperature of about 15 C. at atmospheric pressure indicates the presence oi less than about one per cent of impurities, such methyl alcohol and triuorotrichloroethane.

A portion of the stream in conduit 23 may be discarded by rneans not shown in order to prevent the build-up of contaran ants in the systeni, such as lay-products and polymers formed during the dehalogenation. This stream may he treated, if desired, to recover valuable oy-products. Liquid can also be Withdrawn directly from dehalogenator through outlet conduit l lor the above purposes.

ln some instances it may he desirable to use a soluble stabilizer or inhibitor to prevent oxidation and/or polymerization of the monomer during distillation and storage. Such soluble inhibitors comprise a tertiary amine or terpene.

Condensate from accumulator 2i is passed through conduit 25 to a second fractional distillation column 27:) in which solvent and unreacted halocarbon are removed from the monomer. In column 26 the control of temperature and pressure conditions is more selective than in column le in order to make a closer cut between the monomer and the undesired components, such as the solvent and saturated halocarbon. The temperature and pressure are selected such that the monomer is removed overhead through conduit 23 and is passed through a cooler to an accumulator Sti. Ccndensate at a temperature of about 28 C. is returned to the top of column 2li through conduit 32 as redux. Solvent and saturated halo-carbon are removed as a bottoms product through an outlet conduit When operating at approximately atmospheric pressure the top temperature of column 2e is about 26 C. and the kettle temperature or colurin 2e is about --2l C. Element comprises a conventional heat exchange means, such as an internal coil or an external reboiler, for maintaining the desired temperature at the bottom oi column 25. A refrigerant, such as a light naphtha, is circulated through coils 'il at about --.5 C. Solvent and unreacted monomel1 from reactor Il@ which have been separated from the solid polymer product in separators 5l and 5d are introduced into the lower portion. of column 2G through conduit el. The solvent used in the polymerization for dissolving the polymerization promoter and its recovery will ce discussed. more fully hereinafter. Since the polymerization solvent is also higher boiling than the monomer, it is removed with the bottoms product t rough outlet conduit For operating distillation column 25 at a top temperature of 25 C. and at a kettle temperature of about 2o" C. at atmospheric pressure and.A ior louv temperature polymerization to produce a polymer, analysis o1" a typical monomer overhead fraction indicates the presence of less than 0.065 volume per cent of impurities, such as methyl alcohol as water. The bottoms product from column 2E comprises as its major component trichloroiluoromethane, the solvent used in the polymerization step.

The liquid bottoms product from distillation column 2t continuously passes through conduit to a third fractional distillation column 3d in which the solvent used in the polymerization step, such as CClsF, separated from saturated halocarbon (Cz'aCle) and solvent (methyl alcohol) used in the dehalogenation reaction. Temperature and pressure conditions of distillation column are such that trichlorouoromethane is passed overhead while trichlorotriiiuoroethane and any remaining methyl alcohol are removed as a hott nis product. When using atmospheric pressure in distillation column Se, the kettle temperature will he about e8" C. the overhead teniperature will he aoout 2T C. for separating trichlorofluoromethane from trichlorotriiluoroethane. For superatmospheric pressures higher temperatures are used. The trichlorotrifiuoroethane-containing bottoms product is removed from column et through outlet conduit El and is continuously returned by means of a pump (not shown) through conduit 2li to dehalogenator e. Element Sil is a conventional heat exchange means, su-"h as an internal coil or external rel oiler. for controlling the l-:ettle teinpcrature of distille" 'Ihe overytion column head product comprising tricliloroluoromethane and less than about one per4 cent of the other components oi the feed is removed from column 35i through conduit liti, a portion of which overhead may oe condensed in a conventional cooler il and returned through conduit to the upper portion of column Zili as redux therefor. The treatment or" the overhead product of column 34 and its return to reactor ad will be discussed more fully subsequently.

The overhead product from the second distillation column 26 in conduit 28 comprises monomer and traces of contaminants, such as methyl alcohol or other oxygen-containing compounds, such as water. This vaporous stream in conduit 28 is passed through a conventional cooler 29 in which the vapors are cooled and condensed and resulting condensate is passed from cooler 29 to an accumulator i. Condensate which is collected in accumulator 30 is returned through conduit 32 to the upper portion of distillation column 26 as liquid reflux for controlling the top temperature thereof. Alternatively or in addition to refluxing with condensate from conduit 32, internal cooling means (not shown) may be positioned within the upper portion of column 26 for causing internal reiluxlng.

If only that much ci the vapors in conduit 28 are condensed as to provide reflux to column 26, the remaining vapors are removed from accumulator S through conduit 3i and are passed through treaters 39 and 4l, which are used alternately, to remove oxygen-containing compounds. While one treater is being used, the other treater is being filled with fresh treating agent or sorbent material or the sorbent material therein is being regenerated 'ireaters S9 and 4i contain suitable material for removing traces of methyl alcohol and other oxygen-containing compounds present in the gaseous stream. Suitable treating agents or sorbents comprise phosphorous pentoxide, silica gel, activated carbon, calcium sulfate and m'xtures thereof; however, various other sorbents may -be used which are known tc those skilled in the art. Treaters 39 and il are used since a monomer of high purity is required in the polymerization of trifluorochloroethylene at a low temperature to produce a normally solid polymer of good physical and chemical properties. Preferably, treaters 39 and contain alternate layers of p-hosphorous pentoxlde and silica gel.

After passage of the monomer stream through treaters 39 or di, the stream is passed through conduit l2 to cooler f3 wherein the gaseous stream is cooled and condensed. From condenser or cooler condensate at the desired temperature is passed to reactor t4. It is advantageous although not necessary to provide a cooled holding tank (not shown) to aid in the regulation of the flow of monomer to reactor dit.

To treat the monomer stream in the liquid condition in treaters 39 and tl, cooler 29 is operated such that substantially the entire effluent stream in conduit 28 is condensed. Condensate from accumulator 36 is then passed through cond uit 38 to treaters 39 and di, which are operated as described with respect to vapor phase operations. ln this modiilcation, cooler i3 may be omitted; however, cooler i3 may be used to further cool the condensate to the desired polymerization temperature after passage through treaters 3S and il without departing from the scope of this invention.

Various methods and procedural steps for recovery and purication of the monomer may be practiced, although each method or procedure is not necessarily equivalent to the others. The steps for recovery and purification of the monomer depicted in the drawing is only one of several which may be followed to obtain a monomer of suihcient purity for producing a plastic 'of good physical and chemical characteristics.

For example, the monomer-containing stream in conduit i3 may be treated with P205 or calcium sulfate prior to fractional distillation thereof and subsequent to distillation the monomer concentrate stream is treated with silica gel, especially where the monomer stream is water washed to remove acidic contaminates, etc. rThe successive steps of treating the monomer stream with a water washing step, P205 or calcium sulfate, and distillation, and treating with silica gel renders a monomer of high purity. Another procedure consists or" the steps of treating the monomercontaining stream of conduit I3 with P205 and then with silica gel. This latter procedure has been found satisfactory for purifying the monomer for subsequent polymerization to solid polymers without distillation. According to the procedure described with reference to the drawing, one of the distillation columns it or 25 may be eliminated without departing from the scope of this invention. The choice of the recovery and purification procedure used will depend upon the economic evaluation as well as such factors as the purity of the monomer desired.

In reactor its, liquid triiluorochloroethylene is polymerized in the presence of a peroxide promoter to produce a plastic polymeric material having good chemical and physical characteristics. A particularly suitable promoter for the production of a plastic product is bis-trichlorocety peroxide. The amount of trichloroacetyl peroxide used varies between about Gl and about 0.15 per cent of the monomer in the reaction mixture depending on the character of the ultimate product to be produced, a preferred concentration being about 0.03 per cent.

Bis-trichloroacetyl peroxide may be prepared by reacting sodium peroxide with trichloroacetyl chloride at a temperature of about -l5 C. rihe bis-trichloroacetyl peroxide product is extracted from the resulting mixture with trichlorofluoromethane. Bis-trlchloroacetyl peroxide is then recovered from the trichloroiluoromethane by crystallization.

Various other organic peroxides, in particular the halogenated acyl peroxides, such as triluoroacetyl peroxide, difluorochloroacetyl peroxide, 2,4 dichlorobenzoyl peroxide, chloracetyl peroxide, bis-triluorodichloropropionyl peroxide, and dichloroiiuoroacetyl peroxide have been found capable of promoting the desired polymerization reaction to produce a normally solid polymer of triuorochloroethylene.

Since the peroxide promoter is solid under normal conditions and substantially insoluble in the monomer, a solvent is used to dissolve the promoter and the resulting solution of the promoter is injected into reactor it through conduit 5l. The use or" the promoter in solution facilitates handling and intimate mixing of the promoter with the monomer in the reaction zone. The preferred solvent is one which is non-reactive and has a boiling point higher than the boiling point of the monomer. The quantity or solvent containing the promoter employed is usually between about 1 and about 20 weight per cent or" the monomer feed but larger or smaller amounts may be used without departing from the scope of this invention. The preferred solvent of the present invention is trichloroiuoromethane. The solution of promoter is maintained at a sunlciently lovv temperature prior to introduction into the reactor to minimize decomposition.

A solution of promoter is continuously or intermittently introduced into reactor at through conduit 5'! after being admixed with fresh or recycle solvent from conduit 55. Alternatively the solution oi promoter may be injected into conduit Ll2 for adniixture with the monomer by means not shown. For the production of a normally solid homopolymer or copolymer a temperature between about 200 C. and about 150 C., preferably below 60 is employed depending upon the promoter and other operating conditions used. Generally, however, somewhat higher temperatures can be used in the process of this invention than are possible for the batch-wise processes described previously. A temperature between about --20o C. and about 25 C. is preferred for the production of a plastic. The pressure should be at least in excess of the vapor pressure of the system at the polymerization temperature employed.

The solid polymer of triuorochloroethylene is formed as nne particles suspended in the liquid monomer because ol its insoluoility therein. The required residence time corresponding to the temperature selected is observed. The formation or the polymer as line particles may be predicated to the fact that triiluorochloroethylene polymerizes by nuclei growth. it is believed that the polymerization of the monomer to the solid polymer is accomplished in a relatively short period of time and that the quantity of polymer produced over a period or time is limited by the rate of formation or" polymer nuclei. As a result the bull; of monomer does not progressively polymerize in entirety. rihis theory is oiiered merely as a means for better understanding the present invention and is not to be construed as limiting the invention or as the only explanation thereoi.

Reactor lll comprises a steel vessel and may be provided with cooling coils or a cooling jacket (not shown) for aiding in the maintenance of the desired temperature therein. The form of the reaction vessel is immaterial from the standpoint of this invention and the vessel may be in the form of elongated tubes or coils through which the reaction mixture flows as a turbulent mixture. As shown in the drawing, however, the reaction vessel is an enlar ed zone in which is contained a substantial quan ty of liquid monomer containing suspended solid polymer. in the enlarged vessel shown, the solid polymer is maintained in suspension by means of a conventional mechanical stirrer 59. Stirrer Eil also aids maintaining uniform temperature throughout the liquid phase in the reaction vessel di. The stirrer 59 may be omitted ii the liquid circulation within the vessel is sufficiently great to maintain the polymer suspended in the liquid monomer, such as the circulation caused by withdrawal and introduction of liquid.

In using a reaction coil or tube of restricted cross section, the iiow through the reaction tube causes sufilcient turbulence or agitation to maintain the solid particles of monomer suspended in the reaction mixture.

ln accordance with this invention, a slurry or" monomer and solid polymer is removed at the appropriate rate to give the proper residence time from reactor d and passed through conduit El by means of pump 551i to cooler 63. This slurry or suspension will contain usually less than l2 weight per cent solids, preferably between about 4 and I weight per cent solids. The slurry may be cooled in cooler t3 to a temperature at least 5 C. below the temperature of reactor s so that vwhen the unreacted monomer is recycled, the

temperature or the reaction vessel is maintained substantially constant at the desired value by controlling the amount of heat removed in cooler 63. From cooler @3 the cooled slurry is passed through either one of separating zones 61 and 68 through conduits and 65, respectively. Separation units tl and ES are used alternately. While one separating zone is on processlow the solid polymer is being removed from the other separating zone. Any of the conventional filter means may be used for separating the solid polymers from the unreacted monomer. Such filter means may comprise a conventional plate and frame nlter press, a leaf filter, a rotary continuous filter, such as those disclosed in Elements of Chemical Engineering, Badger and McCabe, McGraw-Hill Bock Company (1936 second edition. When a continuous filter is used, dual filters are unnecessary. On the other hand, separators Si and 63 may comprise a spray drier or a settling zone in which the solid polymer is settled from the monomer and accumulates in the bottom of the settling vessel from Where it is removed through a suitable star valve or the like. In the diagrammatic illustration shown in the drawing, the solid polymer is removed from separators di and til through outlet conduits S9 and i i, respectively.

Unreaoted monomer is passed from separators Si and 63 through conduits 'l2 and i3, respectively, and is recycled to reactor @A through conduits lll, 'i8 and i9. A portion ci the recycled monomer is returned to the puriiication steps, such as to distillation column 2li 'through conduit si, in order to repuriiy the monomer. Usually the ratio of the amount of monomer recycled to that diverted to distillation column 26 is about 1:1 to about 16:1 by volume or higher, preferably a ratio of about 3:1 to about 4:1.

Since acidic impurities, such as trichloroacetic acid, phosgene and their derivatives, contaminate the monomer-containing stream, it is desirable to remove these contaminants in order to prevent their build-up in the system and to prevent their adverse effect on the physical and chemical qualities of the solid polymer product. Such acidic impurities may be removed from the recycle monomer streani by passing the stream through a treater lt containing a suitable acid absorption medium, such as sodium or potassium hydroxide. A portion oi the stream may by-pass treater 'it by means oi conduct ll, if desired. lf the monomer stream is treated in treater 'it with an aqueous alkali solution, driers containing calcium sulfate (not shown) must be provided for removing traces of aqueous solution from the treated stream.

The monomer-containing stream in conduit 8l contains the solvent used for dissolving the promoter and in the particular embodiment ol the invention described the solvent is trichlorofluoromethane. When the monomer containing stream in conduit Si is introduced distille.- tion column 25, the monomer is removed overhead as previously described and the solvent is removed with the bottoms product through outlet conduit 33. This bottoms product from distillation column 26 is passed to a third distillation column Sli as previously discussed. 'ln distillation column 35i, trichloroiiuoromethane is continuously recovered as an overhead product and is passed through conduit 2S to a conventional cooler Lil in which at least a portion of the vaporous overhead product is condensed. Condensate is then passed to accumulator til. From accumulator fili condensate is recycled to the upper portion or" column 34 through conduit i9 as liduid reflux therefor. When the entire overhead product is condensed in cooler Il? condensate is passed from accumulator 48 through conduit 5l to treaters 53 and 5ft to remove oxygen-containing compounds. When only the amount of overhead required for reflux in column 34 is condensed, the uncondensed overhead product is passed through conduit 52 through treaters 53 and G. Treaters 53 and 54 are operated similarly and contain similar treating materials as were used in treaters 39 and fil for removal of traces of methyl alcohol solvent which inhibits the polymerization reaction. As in the case of treaters te and si, treaters 53 and ed are used alternately, while one is being regenerated or refilled the other is on process flow.

Substantially pure trichlorofluoromethane is returned to conduit 5l for admixture with promoter and for the subsequent introduction into reactor liti through conduit 5l.

Continuous removal of a slurry or suspension from reactor llt and recovery of solid polymer from the slurry is the preferred method of operation in polymerizing triuorochloroethylene, but other methods may be used without departing from the scope of this invention. For eX- ample, a raking or elevating mechanism could be provided in the reaction vessel operating on a sloping bottom to remove the polymer particles as they settle to the bottom. Another modication is a rotating drum containing liquid monomer with a scraping means for removing the deposited polymer from the sides of the rotating drum. The solid polymeric product recovered at 6d and li may be subjected to further treatment, such as fluorination, pyrolysis, drying, etc., without departing from the scope of this invention.

In copolymerization of triuorochloroethylene with another similar comonomer, the comonomer is prepared and purified in a series of steps similar to those used for triuorochloroethylene in separate equipment. The comonomer is then introduced into the polymerization zone either separately or together with triiluorochloroethylene. Where the boiling point of the comonomer is appropriate, the comonomer may be prepared and purified simultaneously and in the same equipment with triiuorochloroethylene.

Various modilcations and alterations oi equipment, such as elimination of one of the distilla-r tion steps, changes in the sequence of purication steps, and changes in the shape and/or size of reactor dil, may be practiced without departing from the scope of this invention. Certain pieces of apparatus and auxiliary equipment, such as liquid level controls, flow controls, temperature and pressure controls, valves, pumps, coolers or condensers and storage facilities have been omitted from the drawing as a matter of convenience and clarity.

Having described my invention, I claim:

l. A continuous process for copolymerizing trifluorochloroethylene with another halogenated olefin substituted only with halogen and at least one uorine atom and containing no more than one hydrogen atom per carbon atom to produce a normally solid copolymer of good physical and chemical characteristics which comprises the successive steps of introducing liquid trifluorochloroethylene and said halogenated olefin and a solution of trichloroiluoromethane and trichloro-A acetyl peroxide into a reaction zone, the amount of trichloroacetyl peroxide being between about 0.01 and about 0.15 per cent of the monomer charged, polymerizing the monomers at a temperature between about -20 C. and about 25 C.

and a corresponding pressure sumcient to maintain the system in the liquid phase in said reaction zone to produce particles of solid copolymer, agitating the reaction mixture to form a slurry of solid copolymer and liquid monomer, continuously withdrawing from said reaction zone a slurry of monomer and solid copolymer, cooling the withdrawn slurry at least 5 C. below the prevailing temperature of said reaction zone, separating by filtration solid copolymer as the product of the process and unreacted monomer from said slurry, treating at least a portion of the unreacted monomer thus recovered from the slurry with an alkali metal hydroxide to remove acidic impurities therefrom and recycling purined monomer to said reaction zone as feed thereto and as a means for controlling the temperature thereof.

2. A continuous process for copolymerizing trifluorochloroethylene with another halogenated olefin substituted only with halogen and at least one fiuorine atom and containing no more than one hydrogen atom per carbon atom to produce a normally solid copolymer which comprises the successive steps of introducing trifluorochloroethylene and said halogenated olen and a solution of trichloroluoromethane and trichloroacetyl peroxide into a reaction zone, polymerizing the monomers at a temperature between about 26 C. and about 25 C. and at a pressure to maintain the system in the liquid phase at said temperature in said reaction zone to produce particles of solid copolymer, forming a slurry of solid copolymer with liquid monomer in said reaction zone, continuously withdrawing from said reaction zone a slurry of monomer and solid copolymer, cooling the withdrawn slurry below the prevailing temperature of said reaction zone, separating solid copolymer as a product of the process and unreacted monomer from said slurry, treating at least a portion of the unreacted monomer thus recovered from the slurry with an alkali to remove acidic impurities therefrom, and recycling puried monomer to said reaction zone as feed as a means for controlling the temperature thereof.

3. A continuous process for polymerizing trifluorochloroethylene with another halogenated olefin substituted only with halogen and at least one uorine atom and containing no more than one hydrogen atom per carbon atom to produce a normally solid copolymer of good physical and chemical characteristics which comprises the steps of introducing liquid triuorochloroethylene and between 5 and 95 weight per cent of said halogenated olen, and a halogenated peroxide which is effective under the polymerization conditions as a promoter into a reaction zone, polymerizing the monomers at a temperature between about 20 C. and about 25 C. and a pressure to maintain the system in the liquid phase in said reaction zone to produce particles of solid copolymer, agitating the reaction mixture to form a slurry of solid copolymer and liquid monomer, continuously withdrawing from said reaction zone a slurry of said monomer and solid copolymer, separating from said slurry solid copolymer as a product of the process and unreacted monomer, and recycling unreacted monomer to said reaction zone.

4. A continuous process for polymerizing triluorochloroethylene with another halogenated olen substituted only with halogen and at least one uorine atom and containing no more than one hydrogen atom per carbon atom to produce a normally solid copolymer which comprises the steps of introducing trifluorochloroethylene and said halogenated olefin into a reaction zone, polymerizing the monomers at a temperature between about 29 C. and about 25 C. in the presence oi a halogenated acyl peroxide which is effective in the aforesaid temperature range as a prometer for the polymerization at a pressure to maintain the system in the liquid phase in said reaction zone to produce particles of solid copolymer, agitating the reaction mixture to form a slurry of solid copolymer with liquid monomer, continuously withdrawing from said reaction zone a slurry of monomer and solid polymer, separating from said slurry solid copolymer' as a product of the process and unreacted monomer, and recycling unreacted monomer to said reaction zone.

5. A continuous process for copolymerizing trifluorochloroethylene with another nalogenated olefin substituted only with halogen and at least one fiuorine atom containing no more than one hydrogen atom per carbon atom to produce a normally solid copolymer of good physical and chemical characteristics which comprises the Steps of introducing triluorochloroethylene and said halogenated oleiin into a reaction zone, polymerizing the monomers at a temperature between about C. and about 25C C. in the presence of a halogenated acyl peroxide which is effective in the aforesaid temperature range as a promoter for the polymerization and at a corresponding pressure to maintain the monomers in the liquid phase in said reaction sone to produce particles of solid copolymer, withdrawing from said reaction zone a slurry comprising monomer and solid copolymer, separating solid copolymer as a product or" the process and unreacted monomer from said slurry, and recycling said monomer to said reaction zone.

6. The improved process for copolymerizing triiiuorochloroethylene with another halogenated olen substituted only with halogen and at least one fluorine atom and containing no more than one hydrogen atom per carbon atom which coniprises introducing triiuorcchloroethylene and said halogenated olefin into a reaction zone, in said reaction zone polymerizing the monomers in the presence of trichloroacetyl peroxide as a promoter at a temperature between about 20 C. and about C. and at a corresponding pressure sunicient to maintain the monomers in the liquid phase to produce particles of solid copolymer in suspension in liquid monomer at the temperature of polymerization7 and separating and i6 recovering particles of 'solid copolymer from the suspension as a product of .the process.

7. The improved process for copolymerizing triuorochloroethylene with another halogenated olefin substituted only with halogen and at least one flu-crine atom and containing not more than one hydrogen atom per carbon atom which comprises .in a reaction zone copolymerizing trifluorochloroethylene and said halogenated olefin at a temperature between about 20 C. and about C. in the presence of a halogenated peroxide which is eiective in the aforesaid teinperature range as a promoter for the polymerization and at a corresponding pressure suii'icient to maintain the monomers in the liquid phase to produce particles of solid copolymer in suspension in liquid monomer at the temperature of polymerization, and separating and recovering particles of solid copolymer from the suspension as a product of the process.

8. The process or claim 7 in which said halogenated peroxide promoter .is diiiuorochloroacetyl peroxide.

9. The process of claim 7 in which said halogenated peroxide promoter is triiiuoroacetyl peroxide.

lil. The process of claim 7 in which said halogenated peroxide is a fiuorochloropropionyl peroxide.

ll. The process ci claim 7 in which. said halogenated peroxide is a halogenated benzoyl peroxide,

12. The process ci claim 7 in which said halogenated oleiin copolymerized with trifluorochloroethyiene is tetrauoroethylene.

113. The process of claim 7 in which said halogenated olefin copolymerized with trilucrochloroethylene is perfiuorobutadiene.

lei. The process of claim 7 in which said halogenated olefin copolymerized with triuorochloroethylene is yinylidene r'luoride.

l5. The process or" claim 7 in which said halogenated olefin copolymerized with trifluorochloroethylene is triiiuoroethylene.

16. 1The process of claim 7 in which said halogenated olen ccpolymerized with trifiuorochloroethylene is dichloroperfiuoropropene.

References Cid in the file of this patent UNTED STATES PATENTS Number Name Date 2,531,134 Krona et a1 Nov. 21, 1950 2,500,804 Rearick June 17, 1952 

1. A CONTINUOUS PROCESS FOR COPOLYMERIZING TRIFLUOROCHLOROETHYLENE WITH ANOTHER HALOGENATED OLEFIN SUBSTITUTED ONLY WITH HALOGEN AND AT LEAST ONE FLUORINE ATOM AND CONTAINING NO MORE THAN ONE HYDROGEN ATOM PER CARBON ATOM TO PRODUCE A NORMALLY SOLID COPOLYMER OF GOOD PHYSICAL AND CHEMICAL CHARACTERISTICS WHICH COMPRISES THE SUCCESSIVE STEPS OF INTRODUCING LIQUID TRIFLUOROCHLOROETHYLENE AND SAID HALOGENATED OLEFIN AND A SOLUTION TRICHLOROFLUOROMETHANE AND TRICHLOROACETYL PEROXIDE INTO A REACTION ZONE, THE AMOUNT OF TRICHLOROACETYL PEROXIDE BEING BETWEEN ABOUT 0.01 AND ABOUT 0.15 PER CENT OF THE MONOMER CHARGED, POLYMERIZING THE MONOMERS AT A TEMPERATURE BETWEEN ABOUT -20* C. AND ABOUT 25* C. AND A CORRESPONDING PRESSURE SUFFICIENT TO MAINTAIN THE SYSTEM IN THE LIQUID PHASE IN SAID REACTION ZONE TO PRODUCE PARTICLES OF SOLID COPOLYMER, AGITATING THE REACTION MIXTURE TO FORM A 